Production of vat dyestuffs of the benzanthrone series



Patented Mar. 12, 1935 moments-(1m vA'r DYESTUFFOF 1 ,pn szA rnRoNE SERIES. 1

-Heinrich -Ne'resheimer, Ludwigshafen-on-the n a Rhine, Germany, assi'gnor'to General Aniline Works mc New York, N. Y a'corporation of I Delaware Nb Drawing. Application its-al a, 1930, serial; '7 j e No. 426,770. In'German" ;I{ebruary 13; 1929 4 Claims; ,(or- 260-36) The present invention relates tof the produc-' tion of vat dyestuffs of the benzanthrone series. It has already beeniproposed to produce new and valuable vat dyestufis to which the ring 1 system I is comrnon by causing acid condensing agents to act on acylamino 'derivatives' of (2-benzanthronyl) -1'-aminoanthraquinone' (II) the acylamino group or the acyl radicle being replaced by other substituents or by hydrogen if desired. 7 v o r i The simplest representative of this series, the dyestuff having the formula I, dyes cotton dark green shades from a reddish blue vat and dissolves in concentrated sulfuric acid giving a reddish blue coloration; itisfthus entirely different in tinctorial properties from the vat dyestufi obtainable by treating l(2-benzanthronyl) l-aminoanthraquinone (formula -fII) with .1 acid condensing agents according to Example 1 of the Patent No. 1,711,710, which dyestufi gives orange red dyeings from abrown red vat and dissolves in concentrated sulfuric acid giving a red brown coloration. r Y g have nowtfoundqthat not .only' are the vacyl-- amino compounds of (Zebenaanthronyl) :l-aminoanthraduinone converted into d erival-Jives {of i I the dyestufi I by treatment withacid condensing agents, but that dyestuffs to which it is possible,

by reason of their analysis, dyeings and reactions tolassign the same ring system Iare obtainedby,

treating the halogenation products of Z-benznt yl) m n .-e t r i 0n or i s bstitution products with non-alkaline, 'ig'egneutral I or aci d, agents having a dehydrogenating action, particular acid condensing agents; such as for;

example sulfuric acid, chlorosulfonicacidand aluminum chloride, whereby furthersubstitution, for examplefsulfonation or halogenation,- oroxie dation may simultaneously be eiiected.- By:;the term 'halogenation products of (2-benzanthronyl) -1-aminoanthra'quinone or its substitution products I understand the products obtainable" from (2 benzanthronyl) +1-amiridanthra Q quinone or its substitution'products containing 1 halogen or an acylamino group by a treatment with halogen or halogenating agents.

The new dyestuffs mostly crystallize from'organic solvents and 'dye cotton from blue vats yellow-green to blueegrayshades.v

The following examples will further illustrate practice but the invention is not restricted to these examples; The parts are by weight.

Eazdmple 1 7 parts of tribromo-(Z-benzanthronyl) -1- aminoanthraquinone (obtainable by treatment of (2-benzanthronyl)-1-aminoanthraquinone with an excess of bromine without diluents and which crystallizes in the form of orange needles from nitrobenzene) are heatedtofrom to centigrade for about-3 hours with parts of chlorosulfonic acid. The reaction mixture is then diluted with 60 per cent sulfuric acid until the dark blue sulfate of the fnewdyestuff'which has a metallic lustre has. been precipitated. This is 1 then filtered oil and decomposed by treatment with-water; The dyestufi f-thus' obtained isia:

dark .greenpowder, and forms-lemeraldsgreen:

needles when crystallized,from-meta:cres01., It

dissolves in concentratedsulfuric acid giving a yellow-green coloration and dyes- -cotton:--.Iast greenshades irom a'blue vat.

@A dyestuff, probably identical NVitlljjll'lliSQfllSi formed when (Z-benzanthronyl) -1-aminoanobtained, which has been formed from the initial in dichloracetic acid) is heated with chlorosulfonic acid. I

Example 2 10 parts of dibromo -rnonochloro-(2-benzanthronyl)-1-aminoanthraquinone (crystallizing in the form of orange needles from nitrobenzene and obtainable by brominating the condensation product from 1' molecular proportion of 2.6- dichlorobenzanthrone and 1 molecular proportion of l-aminoanthraquinone withan excess of brominein the absence of diluents) are introduced whilestirring at from to centigrade into parts of chlorosulfonic acid, and the reaction mixture is stirred at this temperature until the formation of dyestuif is completed. The dyestuff, which is obtainable in almost a quantitative yield'by pouring the solution into water, is very similar-tothe dyestuff prepared according to the first paragraph of Example 1. i

If fuming sulfuri c'acid (10 per cent) be employed instead of chlcrosulfonic acid, a vat dyestufi is obtained which dyes cotton shades from a blue vat.

Example 3.

A. mixture of 20 parts of 'mono-(Z-benz anthronyl)-1.4-diamino-anthraquinone having the formula p 200 parts of vbenzoyl chloride and 30 parts of bromine are stirred for 2 hours at from 40 to 50 centigrade and then for 2 hours at from to 200 centigrade; after cooling the whole is diluted-with400 parts of nitrobenzene and the gray violet crystalline precipitate is filtered off and washed with alcohol. If the product thus blue-gray I material by the introduction of a benzoyl radicle and two bromine atoms, which can scarcely be vatted and which has no afiinity for the vegetable fibre, be boiled for a short time with nitrobenzene, a yellow green solution is obtained which solidifies to a green crystal pulp when cooled. The new dyestuff, which according to analysis contains two bromine atoms and a benzoylamino group in the molecule and. which must have been formed from the initial material by the loss of two hydrogen atoms, dissolves in concentrated sulfuric acid giving a red-violet coloration and dyes cotton very fast yellow-green shades from a blue-violet vat.

What I claim is:

1. Vat dyestuffs corresponding to the general formula: H r

-Hah wherein 9: stands for one of the numbers 2 and 3 and wherein Y means hydrogen or a benzoylamino group, which dyestuffs. dye cotton from blue vats yellowish green to bluish gray shades.

2. A vat dyestufi corresponding to the formula:

which dissolves in concentrated sulfuric acid giving a yellowish green solution and dyes cotton fast green shades from a blue vat.

3. A vat dyestuff corres'iionding to the formula:

which dissolves in concentrated sulfuric acid 1 giving a yellowish greensolution and dyes cotton from a blue vat fast green shades.

which dissolves in concentrated sulfuric acid giving a reddish violet solution and dyes cotton from a. bluish violet vat fast yellowish' green shades.

HEINRICH NERESHEIMER.

4. A vat dyestuffcorrespondi'ng to the formula: 7 

